TW201030475A - Compositions and processes for photolithography - Google Patents

Abstract

New photoresist compositions are provided that are useful for immersion lithography. In one preferred aspect, photoresist composition are provided that comprise: (i) one or more resins that comprise photoacid-labile groups, (ii) a photoactive component, and (iii) one or more materials that comprise photoacid labile groups and that are distinct from the one or more resins; wherein the deprotection activation energy of photoacid-labile groups of the one or more materials is about the same as or lower than the deprotection activation energy of photoacid-labile groups of the one or more resins. In another preferred aspect, photoresist compositions are provided that comprise (i) one or more resins, (ii) a photoactive component, and (iii) one or more materials that comprise a sufficient amount of acidic groups to provide a dark field dissolution rate of at least one angstrom per second.

Description

W 201030475 VI. Description of the Invention: [Technical Field] The present invention relates to a novel photoresist composition, which is particularly useful for infiltrating micro-shadowing methods. In one aspect, the preferred photoresist composition of the present invention will have a particular developer dissolution rate. In another aspect, the preferred photoresist composition will have a different resin having a different photoacid-iabiie group. [Prior Art] ❹ Photoresist is used to transfer an image to a photosensitive film of a substrate. A photoresist coating is formed on the substrate, and the photoresist layer is then exposed to the source of activating radiation through the reticle. The reticle has regions that are opaque to the activation ray and other regions that are transparent to the activating radiation. Exposure to an activating radiation system provides photoinitiator conversion of the photoresist coating to thereby transfer the pattern of the reticle to the photoresist-coated base-developing photoresist to provide an embossed pattern that allows selective processing of the substrate. US Patent Application No. 246,373. The growth of the swaying conductor industry is driven by Moore's Law (Moh, s hw), which states that the complexity m of the Ic device becomes necessary. The requirements of the pattern and structure of the feature size can also show significant shortcomings, especially for a variety of applications. [At present, quarter-micron and even sub-high resolution] [Summary] The formation of micro-uncharacteristics. ~于-..' We now offer new heart compositions and methods. 94780 3 201030475 More particularly, in one aspect, a preferred photoresist may comprise (i) one or more resins comprising a photoacid labile group, (ii) a photoactive component, and (iii) a photoacid. An unstable group and one or more materials different from the one or more resins; wherein the photoprotective activation energy of the photoacid-labile group of the one or more materials is about equal to or lower than the photoacid instability of the one or more resins The group deprotects the activation energy. Preferably, the one or more materials are substantially incompatible with one or more resins. In this aspect, it is also preferred that the deprotection activation energy of the photoacid-labile group of one or more materials is lower than the deprotection activation energy of the photoacid-labile group of the one or more resins. For example, a photoacid-labile group of one or more materials is derived from the reaction temperature of a photoacid-labile group of one or more resins (especially deprotected to provide a group having a higher acidity such as -C00H). Low temperature reaction (especially deprotection to provide groups with higher acidity such as -C00H) (this lower temperature, for example, at least 5 ° C, 10 ° C, 15 ° C, 20 ° C, 25 ° C, 30 °C, 35°C, 40°C, 45°C or 50°C or lower). These differences in reactivity can occur during the post-exposure baking step of the photoresist layer during lithography. For example, in one embodiment, the one or more resins may comprise an ester photoacid-labile group (eg, may be provided by polymerization of a third butyl acrylate), and one or more materials Containing an acetal photoacid-labile group. In another embodiment, one or more resins and one or more of the 4 94780 201030475 materials may each comprise a photoacid non-tetra group, but the one or more materials will comprise a more highly branched a more highly branched carbon chain (eg, .-«=〇) 光 R photoacid-labile group, wherein R is a more highly branched ester group of the one or more materials relative to one or more resins) . In another aspect, the photoresist is provided comprising (i) one or more resins, (ii) a photoactive component, and (iii) comprising sufficient amount of a dark field dissolution rate to provide at least one angstrom per second. One or more materials of an acidic group. In this aspect, suitable acidic groups of the one or more materials include, for example, 'one or more materials comprising one or more selected from the group consisting of fluorinated alcohols (eg, (CF3) 2 (〇H)-), sulfonamide , a heterocyclic substituted carbocyclic aryl group (such as a hydrogen naphthyl group), and an acidic group of a carboxyl group (such as -COOH). Preferably, the one or more materials comprise a sufficient amount of acidic groups to provide a dark field dissolution rate of at least two angstroms, three angstroms, four angstroms or five angstroms per second. The amount of acidic groups used to provide the desired dissolution rate of the developer in a particular material, such as a resin, can be determined empirically. As indicated herein, the dark-field developer rate of one or more materials of the photoresist composition is determined as follows: One or more materials are formulated as a fluid composition of 3% by weight in ethyl acetate. The ethyl acetate formulation was applied to a ruthenium microelectronic crystal and the solvent was removed under soft bake conditions (11 {rc, 60 sec) using a vacuum plate. Subsequently, the 0 26 N tetramethylammonium hydroxide developer is used: the soft baked layer is treated in a puddle mode and the layer thickness is measured by standard procedures such as using a quartz crystal microbalance or dissolution rate monitor. Loss of production. 9 ^ 94780 5 201030475 The superior photoresistance of the present invention exhibits reduced defects associated with resist relief images formed from the photoresist composition. In some aspects, micro-bridging between the lines of the formed relief image can be minimized or avoided. In all aspects of the invention, one or more materials are preferably substantially incompatible with one or more resins. As described herein, one or more materials that are substantially incompatible with one or more photoresist resins can be any material that is added to the photoresist to cause a reduction in aqueous alkaline development.适当 Suitable substantially non-mixable materials for use in the photoresist of the present invention include a composition comprising a stone and/or a fluorine substitution. Preferred materials or materials for use in the present invention comprise acidic groups such as carboxyl groups, emulsified alcohols (e.g., (CF3)2C(OH)-), extender amines, and/or heterosubstituted carbocyclic aryl moieties. Also preferred are substantially non-mixable materials containing photoacid-labile groups such as photoacid-labile esters or acetal groups, and photoacid-labile groups include chemistry as described herein. These groups of the resin component of the photoresist are amplified. The preferred substantially non-mixable material for use in the photoresist of the present invention will be dissolved in the same organic solvent used to formulate the photoresist composition. The particularly substantially non-mixable materials used in the photoresist of the present invention will also have a lower surface energy and/or a smaller hydrodynamic volume than one or more resins of the resistive resin component. The lower surface energy promotes segregation or migration of the substantially immiscible material to the top or upper portion of the applied photoresist coating 6 94780 201030475. In addition, a relatively small fluid dynamic volume may be preferred because it promotes the effective migration of one or more substantially non-mixable materials to the upper region of the applied photoresist coating; . High diffusion coefficient) . Preferably, the photoresist used in the present invention is substantially non-mixable in the photoresist developer composition (e.g., G.26N aqueous solution). Because, in addition to the above discussion, the photoacid-labile group is decomposable for its mi,, -, and it has its aqueous alkali-soluble bismuth. Each steel is searched for, such as _CH(CF3)2, base, etc. It is a material that cannot be mixed in quality. = = appropriate material polymerization in the first part of the invention; = = granules can be synthesized to synthesize discrete particles (4) or in combination; (if the wire has a set size and low molecular weight, the two polymer particles can be ❹ In the New Zealand, the average particle size is used: (= = 2, 2, 2, 2, 2, 2, and more preferably about 5 μ, preferably about 1 〇 to about 00 angstrom, or even better, 10 In the form of polymer particles. For most applications, the preferred particle system has an average particle size of less than about 200 or 1 angstroms = another suitable substantially non-mixable of the photoresist of the invention = can have a Si content 'including Shi Xi times Semi-gas fired (s a) material having a group of (10) 2, etc. Preferred materials which are substantially incapable of the material include polyhedral oligomeric oligosaccharides. 94780 7 201030475 Preferred materials include the following: Photoacid-labile groups: As discussed above, in some cases, the acid-labile group can be used as a higher-branched di-branched photo-acid than in the United States.

No. in the road. For example, a suitable branched photoacid-labile group may comprise an optionally substituted alkyl group having about 5 or more carbon atoms, having at least two branched carbon atoms, ie, at least two secondary, tertiary Or a quaternary carbon atom. The base of the hospital can be divided into non-circular green groups and money. Suitable alkyl moieties include those having one, two or more tertiary carbon atoms, and/or one, two or more quaternary carbons. As used herein, "secondary, carbon refers to a carbon atom having two non-hydrogen substituents (ie, g}2RRi, wherein R & Rl are the same or different and each is not hydrogen);" Tertiary, carbon refers to a carbon atom having three non-hydrogen substituents (ie, QHRI^R2, where R,

R1 and R2 are the same or different and each is not hydrogen); and the term "quaternary" carbon as used herein refers to a carbon atom having four non-hydrogen substituents (ie, QJRRfR3 'where R'R1, ^ and R are Same or different and each is not hydrogen). See, for example, Morrison and Boyd, Organic Chemistry, especially on page 85 (third edition, Allyn and Bacon) for their terminology of Levels 2, 3 and 4. It should also be understood that "alkyl" as used herein includes linked or branched carbon chains such as alkylenes, alkylenes and the like. Moreover, for the purposes of this disclosure, ester-bonded ketone carbon (ie, 0 &) is referred to herein as "carbonyl oxygen," while bonded oxygen (ie, 〇〇(〇)) 8 94780 201030475 is incorporated herein. Known as "carboxy oxygen." As described in the above structure, it is generally preferred that the quaternary carbon is directly bonded (ie, covalently bonded without other intervening atoms) to . Acidic Groups: As discussed above, one or more preferred materials for use in the present invention comprise acidic groups such as buffer groups, fluorinated alcohols (e.g., (CF3)2C(0H)-), >6 yellow capacamine And/or a heterosubstituted carbocyclic aryl moiety. These acidic groups are further discussed below. ❾ Carboxyl' These groups include a moiety having a functionality of -C00H, such as a Cl-25 alkyl group substituted with one or more -C00H groups. The preferred photoresist composition of the hydrazine group may comprise one or more materials comprising a sulfonamide group optionally substituted, including a group such as RS(=0)(X)NR'2, wherein R is a non-hydrogen substituent, especially -OH (to provide -S〇3H); _ optionally substituted G-20 alkyl; and electron-withdrawing gro叩, such as halogen, especially I Or a haloalkyl group such as a fluoroalkyl group such as F3C-. In the formula RS(=0)(X)NR' 2, an X-based spacer (such as a chemical bond or a 1 to 8 carbon bond), and each R' is independently a hydrogen or a non-hydrogen substituent, such as An optionally substituted Cud alkyl group for the group defined by R. Therefore, it should be understood that the term "sulfonamide" as used herein is included in the case where the sulfonyl (S〇2) moiety is directly bonded (eg, RS in the formula RS〇0) (X)NR'2 is a chemical bond) Nitrogen, and wherein the sulfonyl (S〇2) moiety is by 1, 2 9 94780 201030475, 3 or more atoms (such as carbon atoms, such as X is (, 〇 ") and continued The nitrogen atom spacing of the amine group is as follows. In some aspects of the invention, it is preferred to include the photoresist composition of the material, wherein the gamma group (10) is composed of two amine groups. 3 yuan of multiple non-nitrogen materials and two amine parts 2# are separated by one. The adjacent nitrogen-substituted heterocyclic carbocyclic aryl group is used to incorporate the preferred substituted carbocyclic aromatic and other substituted carbocyclic aryl moieties, such as a naphthyl group, to azepine naphthyl (aeenaphthyl). , Fickey, etc. Typically, /, 4, and B (e.g., 2 or 3 fused rings, at least one of which is preferably a mixture of two or more ring-bonded carbocyclic aryl groups such as a hetero-substituted anglo-American, a rectangular group) Miscellaneous base, phenanthryl and the like. The butyl, terbene, enyl, ethane naphthalene carbocyclyl groups may have various hetero substituents, and are generally preferably sulfur-containing substituents. For example, preferred miscellaneous 3 = aryl groups of the resins of the present invention include those having one or more of the following, (counter) (= carbocyclic alcohol (e.g., hydroxyCh alkyl), mercaptoalkyl (e.g., HSCl_e) Alkyl), alkane^() such as Ci-e alkyl fluorenyl such as formazan or ethenyl), alkyl sulfides such as alkyl carbides, several acids (including Cl-I2), burning The base bond includes an aryl group of a group such as Ci-B_. The at least one hetero atom of the substituent containing a hetero atom preferably has a hydrogen substituent (e.g., a hydroxyl group is preferred over the alkoxy group). It is also preferred that the hetero atom group has a hetero atom directly bonded to the carbocyclic ring (such as a hydroxyl group or a fluorenyl ring substituent), or the hetero atom is a ring of an activated carbon such as a ring substituent of -CH2aft or :-ch2sh. , or other primary hydroxy or mercaptoalkyl. 10 94780 201030475 A material having a hetero-substituting for use in the photoresist of the present invention (which may or may be a material of a carbocyclic aryl group of a aryl group substituted with a aryl group) may contain, in addition to a substituted element, Provided by the polymerization of a repeating unit, especially a non-aromatic monoaliphatic ring, a heterocyclic alicyclic acid or a cyclic olefin which is optionally substituted, which is a π alicyclic group, such as a poly-:: acid Unstable portion X: Preferably, at least the type (four) repeat unit contains light ((10)) image formation = photoacid instability S or secret portion. For use on 193 nm, except for the avoidance: 2:::: The resin that is not available is the essential aroma. & naphthyl or other hetero-substituted carbon county other than any of the acid-rich livers; or the polymer unit can be provided by an anhydride (such as maleic acid or Ikonic-rhodium polymerization), such as Provided by the polymerization of a suitable propylene (iv) such as propylene sulfonate & lysine, butyl vinegar, etc. The material of the compound (which can have a wide range of heterocyclic carbon ring aryl units in the photoresist) The amount of the material which is unmixable in the permeation may suitably contain a relatively small amount of the upper thiol-based or other hetero-substituted carbon cyclyl. The use of the hydroxynaphthyl unit is exemplified. A good lithographic knot is not miscible; the resin used in the photoresist of the present invention (which may be substantially 50 or 4 Q + material) may suitably contain less than the compound based on the total unit of the resin. Nano, TO _, the percentage of the ear of the hetero-substituted carbocyclic aryl unit, or based on the polystyrene, even less than 30, 20, 15 or 10 mole percent based on the resin. Single morning 兀. Of course 'substantially non-mixable The resin may be 6, 7, or 8 to 70, 'suitably containing about 0.5, 1, 2, 3, 4, 5, 1 a molar percentage of hydroxynaphthyl units. Typically, based on total tree 11 94780 201030475 lipid units, the tree contains up to the hetero-substituted carbon-based unit, 2, 3, 4, or 5 molar percentage units, usually Preferably, the base unit comprises a base unit based on a resin or a 45-substituted heterocyclic carbocyclic aryl 'about 5, 1 G, 2 (), 3 Å, 4 〇 used in the optical plate of the present invention. A preferred material of the naphthyl unit (which may be substantially, a heterocyclic substituted carbocyclic aryl unit imaged and preferably substantially free of material) is attached to other aromatics outside the 193(10) base unit. a base or a heterocyclically substituted carbocyclic aryl having a percentage of less than about 5 moles, in addition to a preferred polymer containing

The aryl group is more preferably an aromatic group other than the carbocyclic aryl unit of the aryl group other than the carbocyclic aryl unit. In addition to the miscellaneous fraction of 2 moles, as discussed by the 'hetero-substituted m-fat unit and the photoresist of the present invention: = 3 = various parts, tree 0^7 / upper, the knives are replaced as needed 〇 "Substituents may be present at one or more of the available positions or at three positions via one or more suitable groups such as: (i.e., θ2 F, Cl or Br); cyano; C _8 alkane .crf its .r ® (especially

a trace of fluorenyl; C2'8 dilute; C2 read; record; nitro; burnt base such as CBu 6 burnt base such as acetamyl and the like. Preferred substituted carbocyclic aryl units for incorporation into the resin are via one or more of a hydroxyl group (-0H), a mercapto group (-SH), an alcohol (e.g., a hydroxy Ci 6 alkyl group), a mercapto group (e.g., HSCh alkyl), alkyl fluorenyl (such as Ch alkyl sulfonyl such as formazan or ethyl ketone), alkyl sulfides such as Cl-6 alkyl sulfide, carboxylic acid vinegar (including vinegar), alkyl ethers including Substituted naphthyl groups such as Cw ether. Preferably, at least one hetero atom of the hetero atom-containing substituent has a hydrogen substituent (e.g., a reduction is preferred over the alkane 94780 12 201030475 oxy group). It is also preferred that the hetero group has a hetero atom directly bonded to the carbocyclic ring (such as a (4) or M-ring ring substituent), or a substituent of the activated carbon atom such as a substituent of -GHm2SH, Base or mercaptoalkyl. ^ Fluorinated alcohol, a wide range of fluorinated alcohol groups can be used, including Π-25 alkyl groups substituted with one fluorine atom. Particularly good fluoroalcoholic system (CF3) 2c (7) magic -. The preferred imaging wavelength of the illuminating micro-m is pure: under-thin (10) © wavelength 248, and sub-200 nm wavelength such as 193 ηιη. In addition to one or more materials that are substantially non-mixable, particularly preferred photoresists of the invention may contain a photoactive component (such as one or more photoacid generator compounds) and one or more resins selected from the group consisting of: 1) It is especially suitable for phenolic resins which are chemically amplified at 248 nm and which are acid-labile groups. Such particularly preferred resins include: 聚合物 a polymer comprising polymerized units of a vinyl phenol and an alkyl acrylate, wherein the fluorene-polymerized alkyl acrylate unit is subjected to a deblocking reaction in the presence of a photoacid. Exemplary alkyl acrylates which can undergo photoacid-induced deblocking reactions include, for example, tert-butyl acrylate, tert-butyl methacrylate, methyl adamantyl acrylate, methyl adamantyl methacrylate And other non-cyclic alkyl acrylates and acrylate alicyclic esters which are capable of undergoing a photoacid-inducing reaction, such as those described in U.S. Patent Nos. 6, 04, 997 and 5, 492, 793. The patent is incorporated herein by reference; ii) optionally substituted vinyl phenyl (such as styrene), and alkyl acrylate 13 94780 201030475 containing vinyl phenol, no hydroxyl or carboxyl ring substituents (eg, The polymer of the polymerized unit of the above-mentioned i) together with the polymer, such as the deblocking group, is as described in U.S. Patent No. 6, 〇42, 997. Citations are incorporated herein; and polymers containing repeating units comprising an acetal or ketal moiety that will react with a photoacid, and optionally aromatic repeating units (such as stupid or phenolic groups); such polymerizations; Has been in the US patent case No. 5, 929, 176 and 6, 090, 526, the above-mentioned two patents are incorporated herein by reference; and the blend of i) and / or ii) and / or iii); a phenolic resin containing an acid labile group, such as a poly(vinylphenol) and a phenolic acid resin which can be used together with a diazonaphthalene photoactive compound for I-line and G-line photoresist, and which has been Descriptions such as those described in U.S. Patent Nos. 4,983,492, 5,310,410, 5,216,111, and 5,529,880; 3) Resins substantially or completely free of phenyl or other aromatic groups, which are particularly useful at sub-200 nm A chemically amplified positive resist that is imaged at 193 nm. Particularly preferred such resins include: i) a ruthenium polymer containing a polymer unit of a non-aromatic cyclic olefin (internal ring double bond) (e.g., optionally substituted decene), as in U.S. Patent No. 5,843,624. No. 6,048,664, the above-mentioned patent is incorporated herein by reference; ii) containing alkyl acrylate units such as tert-butyl acrylate, tert-butyl mercaptopropionate, methyl acrylate Adamantyl esters, hydrazine decyl acrylates, and other non-cyclic alkyl and alicyclic acrylates. These polymers are disclosed in U.S. Patent No. 6,057,083, the disclosure of which is incorporated herein by reference. The above-mentioned all patents contain the polymerized anhydride units (especially the polymerized horses) as described in the above-mentioned patents No. 14 94780 201030475 and U.S. Patent No. 09/143,462. The polymer of I anhydride and/or Ikon _ unit), as disclosed in European Application No. EP01008913A1 and U.S. Patent No. 6,048, 662, the above two patents cited People herein and form; and a square and / or 11) and / or iii) the blend;

4) A repeating unit having a hetero atom (especially oxygen and/or sulfur) (but not an acid anhydride, i.e., the unit does not contain a county ring), and preferably a resin which is substantially or completely free of any aromatic unit. Preferably, the heteroalicyclic unit is combined with the resin spindle, and more preferably, the resin comprises a fused carbon alicyclic unit, for example, by the polymerization of the filament, and/or the acid π, such as Provided by the polymerization of maleic acid if or ikonic acid. Such resins are disclosed in PCt/US 〇 1/u 914 and U.S. Patent Application Serial No. 9/567, the disclosure of which is incorporated herein by reference. The resin used in the layer at the same time. Such resins are disclosed in, for example, U.S. Patent No. 6,683,171; 6) a fluorine-containing resin (fluoropolymer), for example, by tetraethylene, a fluorinated aromatic group such as fluorine-styrene The compound 匕 contains a hexa n: part of the compound or the like provided by the polymerization. Examples of such resins are disclosed in PCT/US99/21912. Preferred photoresist systems of the present invention include both chemically amplified positive and negative acting photoresists. A typical preferred chemically amplified positive resist comprises one or more of the group consisting of a photoacid-labile group such as a photoacid-labile vinegar or an old-fashioned tree. The present invention provides a method for forming a photoresist relief image and a method of using the photoresist production electronic device of the present invention in 94780 15 201030475. The present invention also provides novel articles comprising a substrate coated with the photoresist composition of the present invention. Other aspects of the invention are disclosed below. As discussed above, the superior photoresist of the present invention exhibits reduced defects after aqueous alkaline development. Such defects may include reduction of organic residuals in the area of no photoresist after development and reduction of microbridges between image jams or other features. As discussed above, suitable materials for the photoresist of the present invention that are substantially incompatible with the resist resin component can be readily identified by simple testing. In particular, as referred to herein, a material that is treated in the same manner but does not have a material that is substantially incompatible with the candidate, once substantially developed by aqueous testing, preferably a substantially non-mixable material will Providing the occurrence or amount of defects reduced relative to comparable photoresist. The defect (or no defect) can be evaluated by scanning electron microscopy. The detection of the photoresist in the infiltrating fluid can be carried out as described in Example 2 of U.S. Patent Publication No. 2006/0246373 and includes mass spectrometric analysis of the infiltrating fluid before and after exposure to the photoresist. In this analysis, the infiltrating fluid was in direct contact with the layer of the photoresist composition to be tested for about 60 seconds during the exposure. Preferably, one or more substantially immiscible materials are added to provide at least 1% of the photoresist material present in the wetting fluid relative to the same photoresist that does not employ such substantially immiscible materials (again by mass spectrometry) Preferably, the reduction in acid or organic matter is tested, and more preferably, the one or more substantially non-mixable materials provide at least 20°/v. relative to the same photoresist without substantially non-mixable materials. , 50%, or 100%, 200%, 500% or 1000% of the photoresist present in the infiltrating fluid (again 16 94780 201030475 w acid and / or organic matter) reduction. In the method of analysis described in Example 2 of US Patent Publication No. 2006/0246373, the preferred photoresist of the present invention at 6 〇.7 will result in less than 1.6 X E-10 during the exposure process. (Mole/cm2 ((10)"/sec) photoacid generator material is leached to deionized water or other overcoat wetting fluid. The preferred photoresist of the present invention may have a preferred water contact angle. It is pointed out that the water contact angle such as the static contact angle, the receding contact angle, the forward sliding contact angle, and the static contact angle of the developer can be in accordance with this mouth, etc. 此• this person ❾々Μ/?. and 23(6) The manufacturer disclosed in pages 2721 to 2727 (2〇〇5 years ^ month/december) is determined. The preferred photoresist (determined to be a spin coating by solvent removal by soft bake) will have at least 65. More preferably at least 70. Then retreat. Further, 'preferably substantially non-mixable material (determined as a spin coating to remove solvent by soft bake) will have at least 65., more preferably at least 70. A particularly good material (which may be substantially incompatible with one or more polymers) includes higher order Such as copolymers, terpolymers, tetrapolymers and pentapolymers. Particularly preferred are fluorine-substituted polymers. Preferred fluorine substituents include perfluoro groups such as FsC-, F3CCF2-, and fluorine. Alcohols such as (F3C)2C(〇H)-. One or more materials of preferred resins may have a wide range of molecular weights 'including 1, 〇〇〇 to 100, 〇〇〇, more typical about 1, 〇〇 〇 to about 20,000 or 30,000 Mw. The particularly preferred substantially non-mixable resin used in the photoresist of the present invention includes the following: and the branched vine portion as described below (ie, _C(CH2CH3) (CH3)2, -C(CH2CH3)3, -C(CH(CHs)2)3, 17 94780 201030475 -C(CH3)2CH(CH3)2, etc.) are particularly excellent branch groups:

18 94780 201030475

19 94780 201030475

Here, in each of the above structures, R1 to R3 are hydrogen or methyl. Further particularly preferred substantially immiscible resins for use in the photoresist of the present invention include the following (with the following group one (ethyl)cyclopentyl group being another particularly preferred branch group):

As discussed above, suitable substantially non-mixable materials include Si-containing materials. Optima is a material that is virtually non-mixable, including the nanostructures of 20 94780 201030475, and the products are from the group such as Hybrid Plastics (Fountain Valley

Commercially available to Califonna), Sigma/Aldrich, and the like. Such materials may include molecular oxidation of Si 〇 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽 矽Anthracene, styrene, acrylic, alicyclic such as norbornene. Particles (including organic particles) which are used as materials which are substantially immiscible include Si-containing and disastrous materials having a county substitution. These particles are commercially available or can be readily synthesized, such as by reacting one or more monomers with a crosslinking agent and an initiator compound (if desired). The reactive monomer may have a desired substitution such as fluorine, a Si group, a photoacid-labile group such as a photoacid labile ester or an acetal, and other alkali-soluble groups such as an alcohol. See Example 1 below, which is an exemplary synthesis of such particles produced using a plurality of different monomers, wherein the monomers - provide photoacid-labile groups to the resulting polymer particles.材料 Substantially non-mixable materials can be present in the photoresist composition in a relatively small amount while still providing an effective result. For example, one or more substantially immiscible M (U·heap is based on the total weight of the fluid composition). Suitable amounts are also provided in the examples below. As discussed above, a preferred photoresist system for use in accordance with the present invention comprises a positive or negative chemically amplified photoresist, i.e., a negatively acting resist composition that undergoes a photoacid-promoting crosslinking reaction such that compared to unexposed In the region, the exposed area of the resist coating is less soluble in the developer to dissolve; and the acid, the composition, the acid which is subjected to photoacid promotion, or the composition of the acid is not 94780 21 201030475 Stable base _ The reaction is applied such that the exposed areas of the coating are more soluble in the aqueous developer than in the unexposed areas. A vinegar group containing a covalent bond = vinegar of a tertiary acyclic alkyl group (such as a tert-butyl group) or a tertiary aliphatic group of a carbon (such as a methyl group) is usually used in the photoresist of the present invention. Preferred photoacid-labile groups of the resins employed. The leuco acid labile group will also be preferred. A preferred photoresist of the present invention typically comprises a tree component and a photoactive component. The resin preferably has a functional group which imparts an aqueous developability to the resist composition. For example, 'preferably, a resin binder containing a polar functional group such as a trans group or a (iv) vinegar. Preferably, the resin component is used in the resist formulation in an amount that is achievable by the abundant aqueous test solution. / For imaging at wavelengths greater than 200 nm, such as 248 nm, 'typically preferred phenolic resins. A preferred phenolic resin is a poly(vinylphenol) which can be formed by block polymerization, latex polymerization or dissolution polymerization in the presence of a corresponding monomer. The vinyl phenols suitable for the production of polyvinyl phenol resins can be prepared, for example, by hydrolysis of commercially available coumarin or substituted coumarin, followed by decarboxylation of the resulting hydroxycinnamic acid. Suitable ethoxylated alkenyl phenols may also be prepared by dehydration of their corresponding hydroxy phenols or by hydroxyl groups obtained by reacting a substituted or unsubstituted hydroxybenzaldehyde with malonic acid. Prepared by decarboxylation of cinnamic acid. Preferred polyvinyl phenolic resins prepared from such ethylene phosgenes have a molecular weight range of from about 2,00 Torr to about 6 Torr Daltons. In order to eliminate the wavelength of more than 200 nm, such as 248 nm, the chemically amplified photoresist containing a mixture of a photoactive component and a resin component, the tree t 94780 22 201030475 component contains a phenolic unit and a non-phenolic system. a copolymer of both units. By way of example, one of the preferred groups of such copolymers has substantially, substantially- or all of the acid labile groups on the non-phenolic units of the copolymer, in particular, alkyl acrylate light. An acid labile group, that is, a phenolic-alkyl acrylate copolymer. A particularly preferred copolymer binder has the repeating unit X of the following formula and

Wherein, the entire copolymer site, and R, is a substituted or unsubstituted alkyl group having from 1 to about 18 carbon atoms, more typically from 1 to about £8 to 8 carbon atoms. The third butyl group is generally a preferred R group. R, the group may be optionally substituted with, for example, one or more halogens (especially F, C1 or Br), Ci-s alkoxy, Cm-alkenyl or the like. Single _ X and y may be alternately alternated in the copolymer or may be disposed throughout the polymerization. These copolymers can be easily formed. For example, for the fat of the upper machine, the acetyl group and the substituted or unsubstituted propylene & _ soil may be used as described in the technical field of the present invention. Under the strip, the third ester of acid, etc.) is condensed. The substituted ester moiety, the acid alkyl ester (for example, the acryl acrylate unit is used as a resin acid not ^1^~0~C(=0)~, after exposing the coating containing the photoresist of the resin The photoacid will induce a cleavage, and the copolymer will have a cleavage of from about 8,000 to about 10,000 Å to about 30 Å, and its molecular weight distribution is about 'more, 5, 〇〇〇3 or lower, 201030475 has a molecular weight distribution of about 2 or lower. Non-phenolic resins such as alkyl acrylates (such as tert-butyl acrylate or tributyl methacrylate) and vinyl alicyclic rings ( Copolymers such as vinylnorbornyl or ethenylcyclohexanol compounds can also be used as resin binders in the compositions of the invention. These copolymers can also be polymerized by free radical polymerization or other known Prepared by procedures, and suitably having a molecular weight of from about 8,000 to about 50,000, and a molecular weight distribution of about 3 or less. Acid-depleted desperate segments having positive-acting chemically amplified photoresists for use in the present invention. Other preferred resins of the group are described in European Patent Application No. 0 092 766 A2 to Sh ip 1 ey Company (with acetal) Resin and ketal resin) and Shipley Company's European Patent Application No. ΕΡ 0783136 A2 (terpolymers of terpolymers and other including the following units: 1) styrene; 2) hydroxystyrene; and 3) acid labile The base, especially an alkyl acrylate acid labile group such as: tributyl acrylate or tributyl methacrylate, is disclosed. Generally, resins having a plurality of acid labile groups will be suitable, such as acid-sensitive esters, carbonates, ethers, quinones, and the like. Although a resin having an acid labile group integrated with the polymer backbone can also be used, the photoacid labile group will more typically hang from the polymer backbone. As discussed above, for imaging at sub-200 nm wavelengths such as 193 nm, it is preferred to employ photoresists containing one or more polymers that are substantially, substantially or wholly free of phenyl or other aromatic groups. For example, for sub-200 nm imaging, preferred photoresist polymers contain less than about 5 mole percent aryl groups, more preferably less than about 1 or 2 mole percent aryl groups, more preferably less than about 01。 0. 1, 0. 02, 0. 04 and 0. 08 摩尔% of the aromatic base, and preferably less than about 0. 01 Moer% of the aromatic base. The preferred polymer is completely free of aromatic groups. Aromatic groups 24 94780 201030475 are highly absorbing radiation of -200 nm. Therefore, it is not desirable for polymers used in this short-wavelength 'radiation-imaged photoresist. * Suitable polymers which are substantially or completely free of aromatic groups and which can be combined with the PAG of the present invention to provide a photoresist for sub-200 nm imaging. European Patent Application No. EP 930 542 A1 and U.S. Patent No. As disclosed in 6,692,888 and 6,680,159, the above-mentioned patents are all from Shipley Company °. Suitable polymers which are substantially or completely free of aromatic groups suitably contain © acrylate units (eg photoacid-labile acrylate units) , for example, by a polymerization provider of methyl adamantyl acrylate, hydrazine methacrylate, ethyl decyl acrylate, ethyl decyl methacrylate, etc.; fused non-aromatic alicyclic groups, For example, a polymerization provider can be provided by a norbornene compound or other alicyclic compound having an internal ring carbon-carbon double bond; an acid anhydride, for example, which can be provided by polymerization of maleic anhydride and/or itaconic anhydride; Wait. Preferred negative active compositions of the present month comprise one or more materials which will cure, crosslink or harden upon exposure to an acid (eg, a crosslinking agent component such as an amine based material such as a melamine resin), and the light of the present invention. Active ingredient. A particularly preferred negative-acting composition comprises a resin binder such as a variegated resin, a cross-linking agent, and a photoactive component of the present invention. Such compositions and their use are disclosed in European Patent Application No. 0164248 and No. 0232972, and U.S. Patent No. 5,128,232 to Thackeray et al. Preferred phenolic resins for use as a component of the sapphire binder include phenolic resins and poly(vinyl phenols), as disclosed above. Preferred cross-linking agents include amine-based materials including polycyanide, acetylene urea, benzoguanamine 25 94780 201030475 and urea-based materials. Melamine-furfural resins are generally preferred. Such crosslinkers are commercially available, such as the melamine resins sold under the trade names Cymel 300, Cymel 301 and Cymel 303 by American Cyanamid. The acetylene gland resin sold by American Cyanamid is sold under the trade names Cymel 1170, Cymel 1171, Cymel 1172, the urea resin sold under the trade names Beetle 60, Beetle 65 and Beetle 80, and the benzoguanamine resin under the trade name Cymel 1123. Cymel 1125 is for sale. For imaging at sub-200 nm wavelengths such as 193 nm' better negative effect

The photoresist is disclosed by Shipley Company in WO 03077029. The photoresist of the present invention may also contain other materials. For example, other additives as needed include actinic dyes and contrast dyes, anti-stripe agents, plasticizers, speed enhancers, sensitizers (eg at longer wavelengths such as 365 or G-line wavelengths) In the present invention PAG), etc., in addition to the relatively high concentration, such as 5 to 3% by weight (based on the total weight of the dry component of the barrier), the amount of filler and dye outside the 'this f is difficult to add as needed (four) to low concentration The preferred additive for the resist of the present invention is an additive such as hexamethyleneamine which enhances the resolution of the developed relief image. The addition is suitably in a relatively small amount. For example, about 1 phantom weight _ for PAG), typically 1 to 5% by weight. Other suitable additives include acid =: p-toluene (tetra) iron salt and p-toluene dicyclohexyl salt salt amines such as tris(tetra) and dodecylamine; aryl faces such as amines H wire phenyl)_2_ (4_ secret phenyl) Bingyuan and so on. The composition of the resist of the present invention is typically used in an amount sufficient to render the resist coating 94780 26 201030475 exposure coating developable in an aqueous alkaline solution. More particularly, the tree 'fat adhesive will suitably comprise from 50 to about 90% by weight of the total solids of the resist. Light - The active ingredient should be present in an amount sufficient to produce a latent image in the coating of the resist. More specifically, the photoactive component will suitably be present in an amount of from about 1 to 40% by weight of the total solids of the resist. Typically, a smaller amount of photoactive component will be suitable for chemically amplified resists. The resist composition of the present invention also contains a photoacid generator (i.e., "PAG") which is suitably used in an amount sufficient to produce a © latent image in the coating of the resist upon exposure to activating radiation. A preferred PAG for imaging at 193 nm and 248 nm includes an imido acid vinegar, a compound of the formula:

Wherein 'R is off brain, diamond, base (such as Cl-12) and all-gas alkyl such as perfluoro(Cl-12 alkyl), especially perfluorooctane sulfonate, perfluoroindole Alkane sulfonate and the like. A particularly preferred PAG is N-[(perfluorooctanesulfonyl)oxy]-5-northene-2,3-diimine. The sulfonate compound is also a suitable PAG, especially a sulfonate. Two suitable reagents for imaging at 193 nm and 248 nm are the following PAG 1 and PAG 2 : 27 94780 201030475 1 2

Such sulfonate compounds can be prepared as disclosed in European Patent Application No. 96118111. 2 (Publication No. 0783136), which is a detailed description of the synthesis of PAG 1. It is also appropriate to expose two kinds of rust compounds which are miscible with the anion except for the above-mentioned camphor sulfonate. In particular, preferred anionic groups include those of the formula RS〇3- wherein R is adamantane, alkyl (such as C!-12 alkyl) and perfluoroalkyl such as perfluoro(C^alkyl), especially Fluorooctane sulfonate, perfluorobutyl sulphate, etc. Other known PAGs can also be employed in the photoresist in accordance with the present invention. Especially for 193 nm imaging, in order to provide improved transparency, it is generally preferred to be a PAG that does not contain an aromatic group, such as the imidosulfonate described above.

Q The photoresist of the present invention may also contain other materials as needed as needed. For example, other optional additives include anti-stripe agents, plasticizers, accelerators, and the like. In addition to fillers and dyes which may be present in relatively high concentrations, such as from about 5 to 30% by weight based on the total weight of the dry ingredients of the resist, such optional additives will typically be present in a low concentration in the photoresist composition. In. Photoresists used in accordance with the present invention are typically prepared by known procedures. For example, the resist of the present invention can be prepared as a coating composition by dissolving the components of the photoresist in a suitable solvent such as glycol ether 28 94780 201030475 such as 2-methoxyethyl ether (diethylene glycol diglyme), ethylene glycol monomethyl ether, propylene glycol monomethyl ether; propylene glycol monomethyl ether acetate; lactate ester such as ethyl lactate or methyl lactate, wherein ethyl lactate Preferred; propionate, especially methyl acetonate, ethyl propionate and ethyl ethoxy propionate; Cellosolve esters such as methyl sialoacetate; aromatic hydrocarbons such as Toluene or xylene; or ketones such as methyl ethyl ketone, cyclohexanone and 2-heptanone. Typically, the solids content of the photoresist varies between 5 and 35% by weight of the total weight of the photoresist composition. Blends of such solvents are also suitable.

The liquid photoresist composition can be applied to the substrate by, for example, spin coating, dipping, roll coating, or other conventional coating techniques. When spin coated, the solids content of the coating solution can be adjusted to provide the desired film thickness based on the particular spin coating equipment employed, the viscosity of the solution, the speed of the spinner, and the amount of time allowed for spin coating. The photoresist composition used in accordance with the present invention can be suitably applied to a substrate which is conventionally used in processes involving photoresist coating. For example, the composition can be applied to the Shi Xi wafer for the production of micro-political Chiba or (4) dioxotomy, money, and other products. Also suitable for the use of aluminum-oxidation Lu, Zhonghua gallium, Tao Jing, quartz field, copper, broken ruthenium substrate, photoresist can also be applied to the anti-reflective layer, especially 3 ▲ slave temple, Tanjung organic resistance Reflective display. After the photoresist is applied to the surface, the pot + θ ^ , without any error, can be dried by the addition of solvent. Until preferably, the photoresist coating is non-tacky. Subsequently, the photoresist layer (if the name θ ^ is exposed to the immersion lithography system, that is, the coating layer of the outer coating) ρ which is between the exposed (especially the projection lens) and the coated photoresist Inter-substrate prior tool [two intertwined turbid fluids occupy] The fluid 94780 29 201030475 is such as water or water mixed with one or more additives such as barium sulfate, which provides a fluid with an elevated refractive index. Preferably, the wetting fluid (e. g., water) has been treated to avoid air bubbles, such as degassing the water to avoid nanobubbles. As used herein, "wet exposure" or other similar terms means exposure of such fluid layers (e.g., water or water and additives) between the exposure tool and the coated photoresist composition layer. Depending on the exposure tool and the composition of the photoresist composition, the photoresist composition layer is then suitably patterned to explode to the activating radiation with an exposure energy typically ranging from about 1 to 100 millijoules (mJ)/cm2. Exposure of a photoresist composition to radiation that is activated for use in photoresist, as referred to herein, means that the radiant energy is caused by, for example, a reaction of a photoactive component (eg, photoacid from a photoacid generator compound). Form a latent image in the middle. As discussed above, the photoresist composition is preferably photoactivated by short exposure wavelengths, particularly sub-400 nm, sub-300 nm, and sub-200 nm exposure wavelengths, with I-line (365 nm), 248 nm. And 193 nm and EUV and 157 nm are excellent exposure wavelengths. After exposure, the film layer of the composition is preferably baked at a temperature ranging from about 70 ° C to about 160 ° C. Thereafter, the film is developed, preferably by treatment with an aqueous developer such as a quaternary ammonium cerium oxide solution such as a tetraalkylammonium hydroxide solution; various amine solutions, preferably 0.26 N tetradecyl ammonium hydroxide such as ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine or methyldiethylamine; alkanolamines such as diethanolamine or triethanolamine; cyclic amines such as pyrrole , pyridine, etc. Typically, it is developed in accordance with procedures recognized in the art to which the present invention pertains. 30 94780 201030475 After developing the photoresist coated on the substrate, the substrate to be developed is selectively treated, for example, in the area of the resist, the program known in the art is controlled by & I, The technical field to which the present invention pertains. For the microelectronic base == engraved f-coated substrate area when the jing system includes _ engraving such as == two; == system (four) agent. ‘:::::this=after’, using the known separation procedure, the resist is self-processed. [Embodiment] All documents mentioned in this paper are in (10). BRIEF DESCRIPTION OF THE INVENTION A non-limiting example is disclosed by Wei Ming. The reference to this document is incorporated herein by reference in its entirety. Example 1: Preparation of Carboxyl Resin

A ternary polymer tree rot having the following structure was prepared as follows:

A. monomer and initiator mixture: weighed 7.00 grams (g) of CH3 (CH=CH)C(=0)0CH(CH3)CH2C(CH3)20H (first monomer), 2. 8〇g (CH2=CH)C(=0)0C(CH(CH3))2C(CH3)3 (second monomer) and male 酸酐g acetic anhydride (third monomer), 0·42 g of Trignox- 23 (initiator) and 31 9478 〇 201030475 17 · 0 g of PGMEA (solvent), added to the feed bottle.

B. Reactor: 30 g of PGMEA in the reactor and maintained at 85 ° C

C. Feeds A to B: Feed A to B at a constant feed rate for 120 minutes. 保持 D. Maintain temperature: After feeding A to B, maintain the reactor temperature at 85 ° C for an additional two The reaction temperature was then allowed to naturally cool to room temperature. The carboxyl resin from the reactor can be used in the photoresist composition without further purification. Example 2 Preparation of Additional Carboxyl Resin The following carboxyl resin was prepared by a procedure similar to that of Example 1:

Example 3 Preparation of a hetero-substituted carbocyclic aryl resin A hydroxynaphthyl terpolymer resin having the following structure was prepared as follows: 32 94780 201030475

χ/y/z = Θ5/1025 1. Reactor: Add 20 g of propylene glycol methyl ether acetate (PGMEA) to a 100 ml (mL) flask equipped with a magnetic stir bar and place the flask with reflux condensation 85 of the device. (: In the bath, stir. Rinse the reactor with dry nitrogen. 〇 2. Monomer/initiator solution · Weigh 6.5 g of 4, 4, 4-trifluoro-3-hydroxy-1-indolyl-3- (trifluoromethyl)propyl-2-mercapto acrylate, and 1.0 g of hydroxyvinylnaphthalene and 2.5 g of 2,3,3-trimethyl acrylate are added to a suitable bottle. The singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the Oxygen dodecanoic acid tert-butyl ester (from Trigan® 23 initiator from Noury Chemicals), and Q shakes the bottle to dissolve the initiator. The monomer/initiator solution is placed in an ice bath. 3. Polymerization: Use A suitable feed pump feeds the monomer/initiator solution to the reactor over 90 minutes while maintaining the monomer/initiator bottle in the ice bath. After feeding the monomer/initiator solution, the reaction is carried out with stirring. The reactor was maintained for an additional 3 hours at 85 ° C. The reactor was then allowed to cool naturally to room temperature. The concentration of polymer obtained in the reactor was typically 23 to 25%, Mw: 10, 000 to 12,000. Example 4: Preparation of sulfonamide resin 33 94780 201030475 A sulfonamide copolymer resin having the following structure was prepared as follows:

A. Monomer and initiator mixture: weigh 7.00 g of CH3 (CH=CH)C(=0)OCH(CH3)CH2C(CH3)2〇H (first monomer), 2.80g ❹ (CH2= CH) C (=0) OC(CH 2 ) 2 NHS 〇 2 CF 3 (second monomer), 0.42 g of Trignox-23 (initiator) and 17.0 g of PGMEA (solvent) were added to the feed bottle.

B. Reactor: 30 g of PGMEA was added to the reactor and maintained at 85 ° C

C. Feeds A to B: Feed A to B at a constant feed rate for 120 minutes 〇

D. Maintain temperature: after feeding A to B, the reactor temperature is again at 85 ° C

Q was maintained for an additional two hours, after which the reactor temperature was allowed to naturally cool to room temperature. The sulfonamide resin from the reactor can be used in the photoresist composition without further purification. Example 2: Preparation and Treatment of Photoresist Composition The photoresist composition is prepared by mixing a specific amount of the following materials: 1. Resin composition: based on the total weight of the photoresist composition, 6.79 wt% of the amount of 2-A Benzyl-adamantyl methacrylate/parametric-: face group r-Tt-a* lactone 4 methacrylate/cyano-norbornyl methacrylate terpolymer; 34 94780 201030475 2. Photoacid generator compound: a third butylphenyltetramethylene fluorene perfluorobutane sulfonate in an amount of 0.284% by weight based on the total weight of the photoresist composition; - 3. Alkali additive: Based on the total weight of the photoresist composition, 0.001% by weight of the amount of N-alkyl caprolactam; 4. Surfactant: based on the total weight of the photoresist composition, 0.0071 weight ° / 〇 The amount of R08 (a fluorosurfactant obtained from Dainippon Ink & Chemicals, Inc.); 5. The substantially non-mixable additive: based on the total weight of the photoresist composition, ❹ 0. 213% by weight The polymer of Example 1 prepared as described in Example 1 above. 6. Solvent composition: propylene glycol monomethyl ether acetate to provide about 90% fluid The photoresist composition is spin-coated on a tantalum wafer, dried on a vacuum hot plate to remove the soft board, and then exposed in a immersion lithography process, wherein the aqueous immersion fluid is in direct contact with the dried photoresist layer. In the infiltration system, the photoresist layer P was exposed to a patterned 193 nm radiation at a dose of 24.1 mJ/cm2 (for the control photoresist layer) and 23.4 mJ/cm2. Subsequently, post-exposure baking ( Photoresist layer as in about 120 ° C) and developed using a 0.26 N aqueous aqueous developer solution. To evaluate the leaching of the resist component after post exposure bake and before development, by LC/mass spectrometry (60 seconds) Leaching time test) Evaluate the photoacid and its photodegradation by-products of the infiltrating fluid for the resistant. [Simple description of the diagram] No [Main component symbol description] No 35 94780

Claims (1)

201030475 VII. Patent Application Range: 1. A method for processing a photoresist composition, comprising: (a) applying a photoresist composition to a substrate, the photoresist composition comprising: (1) one or more resins a photoacid-labile group, (ii) a photoactive component, and (Hi) one or more materials comprising a photoacid-labile group and different from the one or more resins; wherein the one or more materials The deprotective activation energy of the photoacid labile group is about equal to or lower than the deprotection activation energy of the photoacid labile group of the one or more resins; and (b) the dip exposure of the photoresist layer to activate the light Blocks the radiation of the composition. 2. The method of claim 3, wherein the one or more materials are substantially non-mixable with the one or more resins. 3. The method of claim 1, wherein the deprotection activation energy of the photoacid-labile group of the one or more materials is lower than the photoacid-labile group of the one or more resins. Protect activation energy. 4. The method according to any one of claims 1 to 3, wherein the one or more resins comprise a photoacid-labile group which is an ester group and does not contain an acetal photoacid-labile group And the one or more materials comprise a photoacid-labile group that is an acetal group. The method of any one of the preceding claims, wherein the one or more materials comprise a photoacid labile group, the photoacid labile group comprising a photoacid of the one or more resins More carbon chain branches of unstable groups. 94780 36 201030475 - %! 6. A method for treating a photoresist composition comprising: (a) applying a photoresist composition to a substrate, the photoresist composition comprising: (i) one or more resins (ii) a photoactive component, and (iii) one or more materials comprising a sufficient amount of acidic groups to provide a dark domain dissolution rate of at least one angstrom per second; and (b) exposing the photoresist layer to activation Radiation of the photoresist composition. 7. The method of claim 6, wherein the one or more materials comprise one or more acidic groups selected from the group consisting of fluorinated alcohols, sulfonamides, heterosubstituted carbocyclic aryl groups, and carboxyl groups. . 8. The method of claim 6, wherein the one or more materials comprise one or more acidic groups selected from the group consisting of (CF3)2C(0H)-, hydroxynaphthyl or C00H. 9. The method of any one of claims 6 to 8 wherein the one or more materials comprise a sufficient amount of acid to provide an eight dark domain dissolution rate of at least two angstroms, three angstroms, four angstroms or five angstroms per second. Group. 10. The method of any one of clauses 6 to 9, wherein the one or more materials are substantially incapable of mixing with the one or more resins. The method of any one of claims 1 to 10, wherein the one or more materials are resins. 12. A coated substrate system comprising: a substrate having: a coating of a photoresist composition, the photoresist composition comprising: 37 94780 201030475 (a variety or resins comprising photoacid An unstable group, (ii) a photoactive component, and (in) one or more materials comprising a photoacid-labile group and different from the one or more resins; wherein the photoacid-labile group of the one or more materials The de-activated energy system is about equal to or lower than the deprotective activation energy of the photoacid-labile group of the one or more resins. 13. A coated substrate system comprising: a substrate having thereon : a coating of a photoresist composition comprising: (i) one or more resins, (ii) a photoactive component, and (ill) comprising sufficient to provide a dark domain dissolution rate of at least one angstrom per second. The system of claim 12, wherein the infiltrating microsphere> fluid is in contact with the top surface of the photoresist coating. To 14 of them The system further comprises an infiltration lithography exposure tool. 16. A photoresist composition comprising: (i) one or more resins comprising a photoacid labile group, (ii) a photoactive component, and (iii) And one or more materials comprising a photoacid-labile group and different from the one or more resins; wherein the photoacid-labile group of the one or more materials is deprived of 947800 38 201030475, the activation energy system is approximately equal to or lower Deprotecting the activation energy of the photoacid-labile group of the one or more resins. -17. A photoresist composition comprising: _ (i) one or more resins, (ii) a photoactive component, and (iii) And one or more materials comprising a sufficient amount of acidic groups to provide a dark zone dissolution rate of at least one angstrom per second. 39 94780 201030475 3. New inventions are provided that are useful for immersion lithography. In one preferred aspect, photoresist composition are provided that comprise: (i) one or more resins that include photoacid-labile groups, (ii) a photoactive component, and (iii) one or more materials that include photoacid labile groups and that are distinct from the one or more resins; the deprotection activation energy of photoacid-labile groups of the one or more materials is about the same as or In the alternative preferred, the photosensitive compositions are provided that comprise (i) one or more resins, (ii) a photoactive component, and (iii) One or more materials that include a sufficient amount of acidic groups to provide a dark field dissolution rate of at least one angstrom per second. IV. Designated representative map: No case in this case (1) The specified representative map is: the () graph. (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention.